Palladium complexes of perylene diimides: Strong fluorescence despite direct attachment of late transition metals to organic dyes

We prepared the first sigma-bonded metal complexes of widely utilized organic dyes, perylene tetracarboxylic acid diimides (PDIs). These 1,7-dipalladium PDI complexes were synthesized by C-Br oxidative addition of 1,7-dibromo-N,N'-dicyclohexyl PDI (Br2PDI) to Pd(0) phosphine complexes bearing triphenylphosphine and bischelating 1,2-bis(diphenylphosphino)ethane (dppe). The structures of Pd-PDI complexes were elucidated by single-crystal X-ray analysis. Surprisingly, despite direct attachement of two late transition metal centers, Pd-PDI systems are highly fluorescent (Phi = 0.65 and 0.22 for triphenylphosphine and dppe systems, respectively). This is rationalized in terms of weak electronic interactions between the metal centers and PDI pi-system, as revealed by TD-DFT calculations.